JP2000347398A - Photosensitive resin laminate and negative image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the photosensitive resin laminate high in sensitivity to light in the infrared region and good in developability and resolution and safe to white light. SOLUTION: The photosensitive resin laminate is obtained by successively laminating a photosensitive layer containing a compound having an ethylenically unsaturated double bond and a photopolymerization initiator and an infrared absorbing dye and a protective layer on a support, and the above infrared absorbing dye is a phthalocyanine type dye and the protective layer has an oxygen permeability of 1×10-15 cm3(STP).cm/cm2.sec.cmHg}.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin laminate which can be used for fine processing such as a lithographic printing plate, printed circuit board, LSI, TFT liquid crystal display, plasma display, and TAB. More specifically, it is possible to directly draw by laser scanning exposure based on digital signals from a computer etc., especially suitable for infrared laser exposure such as semiconductor lasers, solid-state lasers, etc. The present invention relates to a conductive resin laminate.

[0002]

2. Description of the Related Art Lithographic printing plate, printed circuit board, LSI, T
Lithography technology using a photosensitive resin is widely used for microfabrication of FT liquid crystal display elements, plasma displays, TAB, and the like. Image formation for this purpose is generally performed by exposing the image through a mask and forming a pattern using the difference in solubility between the exposed and unexposed areas in the developing solution. Scanning exposure of a photosensitive resin can be directly performed on the basis of digital information such as the above, and not only the productivity but also the resolution and the positional accuracy can be improved.

[0003] As laser light, various light sources from far ultraviolet to microwave are known, but from the viewpoint of laser output, stability, cost, photosensitivity, etc., laser light that can be used for lithography is Ar ion laser, YAG laser. Those that emit infrared light from visible light, such as helium neon laser and semiconductor laser, are promising. For this reason, various compositions having photosensitivity to visible to infrared light have been studied.

As a photopolymerizable composition having photosensitivity to infrared light, a combination of a cationic dye and a borate complex (JP-A-6-59450, JP-A-5-21622)
7, JP-A-5-265204, JP-A-5-265204
247110, JP-A-6-332175), a combination of a photothermal conversion material and an onium salt (JP-A-9-34110, JP-A-9-13400)
No. 9), and a combination of an organic ionic dye and an azobis compound is known. Since these photopolymerizable compositions have a remarkable effect of inhibiting polymerization by oxygen, it is usually essential to provide a protective layer having a high oxygen blocking property on the photosensitive layer.

[0005]

However, none of the photopolymerizable compositions can provide sufficient sensitivity and are not sufficient in terms of stability. In particular, a high-output laser is indispensable for a photopolymerizable composition in which an infrared absorbing dye and a polymerization initiator are combined. Furthermore, even a photopolymerizable composition containing an infrared absorbing dye and a polymerization initiator and applicable to exposure in the infrared region is usually handled not only in the infrared region but also in the visible region. Must be a dark room like a red light, and there is a problem in the work surface.

It is an object of the present invention to 1) have high sensitivity to laser light emitting infrared light, and 2) to easily handle it under an environment such as a white light without preparing a special environment such as a red light. 3) It is to provide a photosensitive resin laminate suitable for laser direct writing, preferably developable with an alkaline aqueous solution, and an image forming method using the same.

[0007]

As a result of intensive studies, the present inventor has found that the protective layer of the photopolymerizable composition is not a common high oxygen barrier property but rather a low oxygen barrier property protective layer of a specific infrared ray. Completed the present invention by finding that the photosensitive resin laminate laminated on the photosensitive photopolymerizable layer is not only excellent in sensitivity and stability, but also surprisingly can be handled in a bright room such as a white light. I came to. That is, the gist of the present invention is a photosensitive resin laminate in which a photosensitive layer containing a compound containing an ethylenically unsaturated double bond, a polymerization initiator and an infrared absorbing dye, and a protective layer are sequentially laminated on a support. In the above, the infrared absorbing dye is a phthalocyanine infrared absorbing dye, and the oxygen permeability of the protective layer is 1 × 10 ⁻¹⁵ ｛cm ³ (STP) · cm / c.
m ² · sec · cmHg｝ or more. Another gist resides in a method for forming a negative image by imagewise exposing and alkali developing the photosensitive resin laminate.

[0008]

Next, embodiments of the present invention will be described in detail. A dimensionally stable plate is used as the support. Examples of such materials include paper, plastic plates or plastic sheets (eg, polyethylene, polypropylene, polystyrene, PET, polycarbonate, nylon, cellulose, etc.), metal plates (aluminum, zinc, copper), and ceramic plates (aluminum oxide, glass, etc.). ), A composite material (epoxy resin plate reinforced with glass fiber, polyimide resin plate), and a plate or sheet on which a metal foil is laminated or metal is deposited. Among these supports, the aluminum plate is preferable because it is extremely stable in dimension and inexpensive, and the plastic sheet is preferable because it is lightweight and has excellent flexibility.

When the photosensitive resin laminate is a photosensitive lithographic printing plate, the support is preferably an aluminum support. Prior to the formation of the photosensitive layer on the surface of the support, usually the aluminum support of the photosensitive lithographic printing plate is used. As a treatment method, a material subjected to a known surface treatment such as a degreasing treatment, a surface roughening treatment (graining treatment), an anodizing treatment, and a water washing treatment is used. 10 mm, preferably 0.1 mm.
About 0.5 to 1 mm, and the surface roughness is JIS
The average roughness Ra specified in B0601 is usually 0.
It is about 3 to 1.0 μm, preferably about 0.4 to 0.8 μm. A dry film used for processing a printed wiring board, a plasma display or the like has a thickness of 10 mm.
A plastic sheet such as polyolefin or PET having a thickness of 200 μm is particularly preferable as the support.

Next, the components constituting the photosensitive layer (photopolymerizable layer) formed on the support will be described. The ethylenically unsaturated double bond-containing compound (hereinafter referred to as “ethylenically unsaturated compound”) contained in the photosensitive layer is a compound having one or more polymerizable ethylenically unsaturated double bonds in the molecule. And various known unsaturated compounds. Among them, compounds having two or more double bonds in the molecule include low molecular weight monomers and oligomers from the viewpoints of crosslinking efficiency, change in solubility and the like, and so-called acrylic monomers are preferable. In addition, the acrylic monomer in this specification includes an acrylic monomer in a narrow sense and a methacrylic monomer.

As the acrylic monomer, an ester acrylate compound obtained by condensing an unsaturated carboxylic acid with an aliphatic alcohol or an aromatic hydroxy compound, an epoxy acrylate compound obtained by adding an unsaturated carboxylic acid to an aliphatic or aromatic epoxy compound, an isocyanate compound Examples thereof include a urethane acrylate compound having an unsaturated hydroxy compound added thereto, a phosphoric ester having a (meth) acryloyl group, and the like, but are not necessarily limited thereto.

Examples of the ester acrylate compound include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate,
Neopentyl glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, glycerin methacrylate (meth) acrylate, trimethylolpropane di (meth) acrylate Trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane ethylene oxide added tri (meth) acrylate, glycerin propylene oxide added Tri (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri Meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexaacrylate, sorbitol tetra (meth) acrylate, sorbitol penta (meth)
Examples include acrylate, sorbitol hexa (meth) acrylate, di (meth) acrylate of tris (2-hydroxyethyl) isocyanurate, and tri (meth) acrylate of tris (2-hydroxyethyl) isocyanurate.

Examples of the epoxy acrylate compound include compounds obtained by adding an α, β-unsaturated carboxylic acid to an epoxy compound having an epoxy ring such as a glycidyl group or an alicyclic epoxy group. As the epoxy compound, the base skeleton to which the epoxy ring is bonded is an aliphatic, aromatic, or heterocyclic ring, or various epoxy compounds having a structure in which these are mixed. Examples of the aromatic epoxy compound include phenol novolak epoxy. Compounds, (o, m, p) -cresol novolak epoxy compounds, bisphenol-A epoxy compounds, bisphenol-F epoxy compounds, and halogenated epoxy compounds such as brominated phenol novolak epoxy compounds, and the like. These compounds may be low molecular weight compounds or oligomers or high polymers that become resins.

Examples of the aliphatic epoxy compound include sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, (poly) glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, neopentyl diglycidyl ether, hexanediol diglycidyl ether, and (poly) Examples include ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, (poly) tetramethylene glycol diglycidyl ether, (poly) pentamethylene glycol diglycidyl ether, and the like. Examples of the epoxy compound having a heterocyclic structure include triglycidyl isocyanurate and triglycidyl tris (2-hydroxyethyl) isocyanurate.

Examples of the alicyclic epoxy compound include Celloxide 2021, 2080, 3000 manufactured by Daicel Chemical Industries, Ltd.
2000, EPOLIDE GT300, GT400 and the like. Α, β-
As the unsaturated carboxylic acid, for example, an epoxy acrylate compound to which (meth) acrylic acid or the like is added as a catalyst with a quaternary ammonium salt or the like can be preferably used, and further, an acid anhydride such as maleic anhydride or tetrahydrophthalic anhydride can be used. Modified epoxy acrylates further modified with

The urethane acrylate compounds include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate,
Aromatic diisocyanates such as 4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, tolidine diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate;
Aliphatic diisocyanate such as 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), ω, ω ′
Alicyclic diisocyanate such as diisocyanate dimethylcyclohexane, xylylene diisocyanate, α,
aliphatic diisocyanate having an aromatic ring such as α, α ′, α′-tetramethylxylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate
4-isocyanatomethyloctane, 1,3,6-hexamethylenetriisocyanate, bicycloheptanetriisocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate and other triisocyanates such as hydroxymethyl (meth) acrylate, hydroxyethyl Examples thereof include compounds obtained by reacting an acrylic compound having a hydroxyl group such as (meth) acrylate. The phosphate ester has a structure in which a part of a hydroxyl group of phosphoric acid such as methacryloxyethyl phosphate, bis (methacryloxyethyl) phosphate, methacryloxyethylene glycol phosphate is esterified (meth) A compound having an acryloyl group is exemplified.

The polymerization initiator is a radical generator that generates a radical directly by irradiation with actinic rays or by an interaction with a sensitizing dye.
No. 33428, British Patent No. 1388492,
Wakabayashi et al .; Bull.Chem. Soc. Japan; 42, 2924 (1969); FCScha
efer et al .; J. Org.Chem .; 29, 1527 (1964) and the like, halogenated hydrocarbon derivatives described in JP-A-59-152396,
JP-A-61-151197, JP-A-63-41484
JP-A-2-249, JP-A-2-4705, Titanocene compounds described in JP-A-5-83588, etc., hexaarylbiimidazole compounds described in JP-B-6-29285 and the like, Examples include an organic boron complex, a carbonyl compound, and an organic peroxide.

Here, specific examples of the halogenated hydrocarbon derivative include, for example, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-
Bis (trichloromethyl) -s-triazine, 2-n-
Propyl-4,6-bis (trichloromethyl) -s-triazine, 2-n-nonyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4 , 6-Bis (trichloromethyl) -s
-Triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) ) -4,6-bis (trichloromethyl) -s-triazine, 2- (2 ′,
4'-dichlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- [1- (P-methoxyphenyl) -2,
4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methylstyryl) -4,6- Bis (trichloromethyl)-
s-triazine, 2- (p-methoxystyryl) -4,
6-bis (trichloromethyl) -s-triazine, 2-
(P-methoxystyryl) -4-amino-6-trichloromethyl-s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl)-
s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl)
-S-triazine, 2- (4-ethoxynaphthyl)-
4,6-bis (trichloromethyl) -s-triazine,
2- [4- (2-ethoxyethyl) naphthyl] -4,6
-Bis (trichloromethyl) -s-triazine, 2-
(4,7-dimethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2-acenaphthyl-
4,6-bis (trichloromethyl) -s-triazine,
2-phenylthio-4,6-bis (trichloromethyl)
-S-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2-methoxy-4-methyl-6-trichloromethyl-s-triazine, 2,4,6-tris (tribromo Methyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6-bis (tribromomethyl) -s-triazine, 2-amino-
Examples include s-triazine compounds such as 4-methyl-6-tribromomethyl-s-triazine, and among them, bis (trichloromethyl) -s-triazine compound is preferable.

As the titanocene compound, specifically, for example, dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,4-
Difluorophenyl), dicyclopentadienyl titanium bis (2,6-difluorophenyl), dicyclopentadienyl titanium bis (2,4,6-trifluorophenyl), dicyclopentadienyl titanium bis (2,3 , 5,6-tetrafluorophenyl), dicyclopentadienyltitanium bis (2,3,4,5,6
-Pentafluorophenyl), di (methylcyclopentadienyl) titanium bis (2,6-difluorophenyl), di (methylcyclopentadienyl) titanium bis (2,4,6-trifluorophenyl), di (methyl Cyclopentadienyl) titanium bis (2,3,5
6-tetrafluorophenyl), di (methylcyclopentadienyl) titanium bis (2,3,4,5,6-pentafluorophenyl), dicyclopentadienyl titanium bis (2,6-difluoro-3- ( 1-pyrrolyl) phenyl) and the like.

As the hexaarylbiimidazole compound, specifically, for example, 2,2'-bis (o-
Chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (p-chlorophenyl) biimidazole, , 2'-Bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (o, p-dichlorophenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5 , 5'-tetra (p-fluorophenyl) biimidazole, 2,2'-bis (o
-Chlorophenyl) -4,4 ', 5,5'-tetra (o, p-dibromophenyl) biimidazole, 2,
2'-bis (o-chlorophenyl) -4,4 ', 5
5′-tetra (p-chloronaphthyl) biimidazole,
2,2′-bis (o-chlorophenyl) -4,4 ′,
5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, p-dichlorophenyl)-
4,4 ′, 5,5′-tetraphenylbiimidazole,
2,2′-bis (o, p-dichlorophenyl) -4,
4 ', 5,5'-tetra (o, p-dichlorophenyl)
Biimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) -4,
4 ', 5,5'-tetra (o, p-dichlorophenyl)
Biimidazole, 2,2'-bis (o-bromophenyl) -4,4 ', 5,5'-tetra (p-iodophenyl) biimidazole, 2,2'-bis (o-bromophenyl) -4 , 4 ', 5,5'-tetra (o-chloro-p
-Methoxyphenyl) biimidazole, 2,2'-bis (o-methylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-nitrophenyl) -4, 4 ', 5,5'-tetraphenylbiimidazole and the like.

Examples of the organic boron complex include, for example, JP-A Nos. 8-21813, 9-106242, 9-188865, and 9-18868.
No. 6, JP-A-9-188710, and Kunz, Marti
n “Rad Tech'98.Proceeding April 19-22,1998, Chicag
o "and the like, and the organic boron ammonium complexes described in
JP-A-1576232, JP-A-6-175561, JP-A-6-175564, etc., organoboron sulfonium complexes or organoboron oxosulfonium complexes, JP-A-6-175553, JP-A-6-1755
No. 54, the organic boron iodonium complex described in JP-A No. 9-188710, the organic boron phosphonium complex described in JP-A No. 9-188710, JP-A No. 6-348011, JP-A No. 7-1
28785, JP-A-7-140589, JP-A-7-140
No. 292014, JP-A-7-306527, and the like. Specific examples include an organic boron complex having a basic structure represented by the following formula (III).

[0022]

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R ^{1 to} R ⁴ each independently represent an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkaryl group which may have a substituent, or a substituent. An alkenyl group which may be substituted, an alkynyl group which may have a substituent, an alicyclic group which may have a substituent and a heterocyclic group which may have a substituent, wherein R ^{1 to} R ⁴ are They may be linked to form a ring, and X ⁺ represents a cationic group.

From the viewpoints of stability and high polymerization activity, R ¹ to
An aryl group in which three of R ⁴ may have a substituent and a triarylalkyl borate complex in which one is alkyl are preferred. Aryl group is preferably a phenyl group, an alkyl group preferably an alkyl group of C ₁ -C _10. Further, those in which the aryl groups bonded to boron have a chemical bond as described below are also preferable.

[0025]

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(Where R represents an alkyl group) As the cationic group, JP-A-62-143044 discloses
Those having absorption in the visible light region, such as the cationic dyes described in JP-A-62-150242, are not preferable from the viewpoint of stability, and those having as little absorption as possible in the visible light region are preferable. For example, ammonium, phosphonium,
Examples include onium cation groups such as arsonium, stibonium, oxonium, sulfonium, selenonium, stannonium, and iodonium, and transition metal coordination cation complexes. If the specific chemical structure is illustrated, for example, the following compounds can be mentioned.

[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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The absorption maximum of the organoboron complex of the present invention is 40
It is more preferably 0 nm or less from the viewpoint of handleability under a white lamp. Specific examples of the carbonyl compound include benzophenone such as benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-carboxybenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, and Michler's ketone. Derivatives, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 1-hydroxy-1- (p-dodecylphenyl)
Ketone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-trichloromethyl-
(P-butylphenyl) ketone, α-hydroxy-2-
Acetophenone derivatives such as methylphenylpropanone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, thioxanthone,
Thioxanthone derivatives such as ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, ethyl p-dimethylaminobenzoate, p-diethylamino Benzoic acid ester derivatives such as ethyl benzoate are exemplified.

As the organic peroxide, specifically,
For example, methyl ethyl ketone peroxide, acetylacetone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, 3,
Ketone peroxides such as 3,5-trimethylcyclohexanone peroxide, 3,5,5-trimethylhexanoyl peroxide, succinic acid peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-toluoyl Diacyl peroxides such as peroxide, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide,
p-menthane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,
Hydroperoxides such as 1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, 1,3 (or 1,4) -bis (T-
Butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, etc. Dialkyl peroxides,
1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,3
Peroxy ketals such as 5-trimethylcyclohexane, 2,2-bis (t-butylperoxy) butane, t
-Butyl peroxy acetate, t-butyl peroxy octoate, t-butyl peroxy pivalate, t-
Alkyl peresters such as butyl peroxy neodecanoate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxy laurate, t-butyl peroxy benzoate, di-2- Ethylhexylperoxydicarbonate, diisopropylperoxydicarbonate, dimethoxyisopropylperoxydicarbonate, di-2-ethoxyethylperoxydicarbonate, bis (3-methyl-3-methoxybutyl) peroxydicarbonate, t-butylperoxide Peroxycarbonates such as oxyisopropyl carbonate, and 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3 ′,
4,4′-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (t
-Octylperoxycarbonyl) benzophenone,
3,3 ′, 4,4′-tetra (cumylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (p-isopropylcumylperoxycarbonyl) benzophenone, 3,3 ′, 4,4 ′ -Tetra (aminoperoxycarbonyl) benzophenone, carbonylbis (t-butylperoxy dihydrogen 2-phthalate), carbonyl bis (t-hexylperoxy dihydrogen 2-phthalate) and the like.

Among the above-mentioned polymerization initiators, an organic boron complex is preferable, and among them, an organic boron ammonium complex can be mentioned as a particularly preferable polymerization initiator. In the present invention, the infrared absorbing dye needs to be a phthalocyanine infrared absorbing dye. Other than the phthalocyanine-based infrared-absorbing dye, the sensitivity is poor, which is not preferable.

The phthalocyanine infrared absorbing dyes include
JP-A-64-60660, JP-A-1-0017
No. 1, JP-A-3-31247, JP-A-4-1
5263, JP-A-4-15264, JP-A-4-4-1
No. 5265, JP-A-4-15266, JP-A-2-138382, JP-A-3-77840,
JP-A-3-100066, JP-A-4-34816
No. 8, JP-A-60-23451, JP-A-61-164
JP-A-215662, JP-A-61-215663, JP-A-63-270765, JP-A-1-28
7175, JP-A-2-43269, JP-A-2-296885, JP-A-3-43461, JP-A-3-265664, JP-A-3-265
665, JP-A-1-108264, JP-A-1-108265, JP-A-10-182959, JP-A-10-120927, and JP-A-9-2
02860, JP-A-8-325468, JP-A-8-225751, JP-A-8-120186
And the phthalocyanine and naphthalocyanine compounds described in Japanese Patent Application Laid-Open (JP-A) No. 10-205,086.

The photosensitive resin laminate of the present invention has a
The phthalocyanine-based compound preferably has an absorption maximum in a range of 750 nm to 1200 nm because it is advantageous for exposure to light having a wavelength of m or more. Specifically, it is a compound having a phthalocyanine basic skeleton represented by the following formula (I) or (II), wherein the absorption maximum is controlled within the above range by the type of the substituent on the aromatic ring or the type of the central metal.

[0038]

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[0039]

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As the central metal M, an alkali metal (I
a), alkaline earth metal (IIa), IIIb, IVb group, V
Group b, VIb, VIIb, VIIIb, Ib, IIb,
Various metals of Group IIIa, Group IVa, Group Va, lanthanides and actinides are mentioned. As a substituent, an alkyl group,
Alkoxy group, aryl group, halogen atom, nitro group,
Examples thereof include a cyano group, an amino group, an alkoxycarbonyl group, a vinyl group, a carboxyl group, an acryloyl group, and a thioether group. These substituents may be condensed to form a ring. Specifically, if the chemical structure is exemplified together with the absorption maximum (λmax), the following compounds are exemplified.

[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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The preferred proportions of the ethylenically unsaturated compound, the polymerization initiator and the phthalocyanine infrared absorbing dye constituting the photosensitive layer described above are 10
5 to 40 parts by weight, preferably 5 to 30 parts by weight, of the polymerization initiator with respect to 0 parts by weight,
-30 parts by weight, preferably 5-25 parts by weight.

In the present invention, the photosensitive layer described above may contain an alkali-soluble resin as a binder. The inclusion of an alkali-soluble resin is preferable because it improves the coating properties, developability and the like. Examples of such an alkali-soluble resin include a vinyl resin having a carboxyl group and a phenol resin having a phenolic hydroxyl group.

Examples of the vinyl resin having a carboxyl group include vinyl monomers having a carboxyl group such as (meth) acrylic acid, maleic anhydride and crotonic acid, and styrene.
α-methylstyrene, vinylphenol, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth)
Butyl acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate,
Dodecyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, acrylonitrile, vinyl acetate, acrylamide , N-methylolacrylamide, glycidyl (meth) acrylate and the like are preferably used.

As the vinyl resin having a carboxyl group, a (meth) acrylic resin containing (meth) acrylic acid as an essential component is particularly preferable.
Resin acid value is 30 to 250 KOH.
mg / g, molecular weight of 1,000 to 300,000, more preferably 150 in terms of weight average molecular weight in terms of polystyrene by gel permeation chromatography (GPC).
It is in the range of 0 to 200,000.

The above vinyl resin is disclosed in JP-A-4-345.
609, JP-A-6-138659, JP-A-5-586
As described in JP 19467 and JP-A-6-11831, an epoxy compound containing an ethylenically unsaturated double bond such as glycidyl methacrylate or 3,4-epoxycyclohexylmethyl acrylate is added to a carboxyl group to form a resin. Unsaturated groups may be introduced into the chain. By introducing unsaturated groups into the resin side chains, heat resistance, chemical resistance,
Such a resin is preferable because printing durability, sensitivity, adhesion, and the like can be improved. In particular,
An ethylenic alicyclic epoxy compound represented by 4-epoxycyclohexylmethyl acrylate is preferable because of its large effect.

Examples of the phenolic resin having a phenolic hydroxyl group include phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5
-Xylenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, propylphenol, n-butylphenol, t-butylphenol,
-Naphthol, 2-naphthol, 4,4'-biphenyldiol, bisphenol-A, pyrocatechol, resorcinol, hydroquinone, pyrogallol, 1,2,2
At least one phenol such as 4-benzenetriol and phloroglucinol is converted to an aldehyde such as formaldehyde, paraformaldehyde, acetaldehyde, paraaldehyde, propionaldehyde, benzaldehyde, and furfural, or acetone, methyl ethyl ketone under acidic catalyst. A novolak resin polycondensed with at least one of ketones such as methyl isobutyl ketone, a resol resin polycondensed in the same manner except that an alkali catalyst is used instead of an acid catalyst in the polycondensation of the novolak resin, and For example, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, dihydroxystyrene, trihydroxystyrene, tetrahydroxystyrene, pentahydroxystyrene, 2- (o-hydroxystyrene) Rokishifeniru) propylene, 2
-(M-hydroxyphenyl) propylene, 2- (p-
(Hydroxyphenyl) Polyvinyl phenol resin obtained by polymerizing one or more hydroxystyrenes such as propylene in the presence of a radical polymerization initiator or a cationic polymerization initiator, and the like, and these have a weight average molecular weight of 1, Preferably it is 500 to 50,000.

When the alkali-soluble resin described above is incorporated into the photosensitive layer, the ethylenically unsaturated compound 100
It is 50 to 500 parts by weight of the alkali-soluble resin based on parts by weight. A major feature of the present invention is that a protective layer having a low oxygen-blocking property is provided on a photosensitive layer containing a phthalocyanine infrared absorbing dye. Heretofore, since a photopolymerizable composition is cured by radical polymerization, a protective layer having a high oxygen barrier property has been required to minimize the influence of oxygen as a polymerization inhibitor. Surprisingly, the photosensitive layer of the present invention has a very small effect of inhibiting polymerization by oxygen even though it is considered that curing basically proceeds by radical polymerization, and is sufficiently high even with a protective layer having a low oxygen barrier property. Sensitivity is obtained, and when a protective layer with low oxygen barrier properties is used, fog (development residue due to weak curing reaction) does not occur even in the situation where visible light is irradiated, and handling under white light Also found that it would be possible. This is presumed to be because oxygen in the atmosphere, which transmits a small amount of polymerization radicals generated by visible light irradiation from the protective layer, quench effectively, thereby suppressing the curing reaction leading to fog and stabilizing the photosensitive layer. Is done.

One of the indexes of the low oxygen barrier property of the protective layer provided on the photosensitive layer is the oxygen permeability, and the protective layer of the present invention is 1 × 10 ⁻¹⁵ (cm ³ (STP) ・ Cm / cm ²・ sec ・
cmHg) or more. The oxygen transmission rate (P) is determined by POLYMER HANDBOOK (J. BRNDRUP
)), And are known physical properties described in the following formula.

[0055]

P = (Q × L) / (△ P × A × t) Q: Oxygen permeation amount (cm ³ (STP)) L: Film thickness (cm) A: Film area (cm ² ) t: Time (Sec) ΔP: differential pressure (partial pressure on supply side-partial pressure on permeation side) (cmHg)

The oxygen permeability of the protective layer of the present invention is preferably
Is 1 × 10^-13Or more (cm^Three(STP) ・ Cm / cm^Two・ Se
c · cmHg), more preferably 1 × 10^-12(Cm
^Three(STP) ・ Cm / cm^Two· Sec · cmHg)
The upper limit is not particularly limited, but is preferably 1 × 10
^-12(Cm^Three(STP) ・ Cm / cm^Two・ Sec ・ cmH
g) or less, more preferably 1 × 10^-3(Cm^Three(STP) ・
cm / cm^Two.Sec.cmHg) or less.

Another index of the low oxygen barrier property of the protective layer of the present invention is that the oxygen permeability is higher than that of polyvinyl alcohol (however, the film thickness is the same). That is, polyvinyl alcohol is an organic polymer compound having high oxygen barrier properties, but any film formed of an organic polymer having higher oxygen permeability may be used. The material for the protective layer of the present invention is not particularly limited as long as it has the above-described oxygen permeability.For example, cellulose, polyvinylpyrrolidone, gelatin, polyacrylic acid, partially saponified polyvinyl acetate,
Water-soluble polymer compounds such as polyacrylamide and vinylpyrrolidone / vinyl acetate copolymer, and water-insoluble polymer compounds such as polyethylene, polypropylene, polyethylene terephthalate, polystyrene, polycarbonate, nylon, polyamide, and silicone can be exemplified.

In the case of a high oxygen barrier polymer compound such as polyvinyl alcohol, an organic compound or an inorganic compound having a function of improving the oxygen permeability of the polymer compound may be blended, or radiation or the like may be used. It is also useful to form fine pores by using to improve oxygen permeability.

Specific examples of organic compounds that improve oxygen permeability include water-soluble polymers such as polyvinylpyrrolidone, gelatin, polyacrylic acid, partially saponified polyvinyl acetate, and polyacrylamide, and low-molecular-weight compounds such as glycerin, pentaerythritol, and alginic acid. Specific examples of the inorganic compound include, but are not necessarily limited to, barium sulfate, barium carbonate, silica, calcium carbonate, talc, and alumina.

As the material of the above-mentioned protective layer, a mixture of polyvinylpyrrolidone, partially saponified polyvinyl acetate or polyvinyl alcohol and a compound having a function of improving the oxygen permeability of polyvinyl alcohol can be removed during development after image formation. Preferred from the viewpoints of point and adhesion, etc.
In addition, polyethylene, polypropylene and polyethylene terephthalate are preferred because they are inexpensive.

The photosensitive resin laminate of the present invention is produced by applying a photosensitive solution obtained by dissolving the components of a photosensitive layer in a solvent onto a support, drying the solution, and then laminating a film serving as a protective layer on the photosensitive layer. can do. Further, the protective layer can be formed by applying and drying the same as the photosensitive liquid.

Here, the solvent is not particularly limited as long as it has a sufficient solubility for the components used and gives good coating properties, and examples thereof include methyl cellosolve,
Cellosolve solvents such as ethyl cellosolve, methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate , Propylene glycol solvents such as dipropylene glycol dimethyl ether, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate, Ester solvents such as methyl 3-methoxypropionate, heptanol Hexanol, diacetone alcohol, alcohol solvents such as furfuryl alcohol, cyclohexanone, ketone solvents such as methyl amyl ketone,
Highly polar solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like, or a mixed solvent thereof, and further a mixture thereof with an aromatic hydrocarbon may be used. The usage ratio of the solvent is usually in the range of about 1 to 20 times by weight based on the total amount of the constituent components of the photosensitive layer.

As the coating method, conventionally known methods, for example, spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, curtain coating and the like can be used. The coating amount varies depending on the application, but as a dry film thickness, 0.1 to 100 g /
m2, preferably 0.5 to 70 g / m2.
It is more preferable to be within the range. The drying temperature at that time is, for example, about 30 to 150 ° C., preferably 4 to 150 ° C.
The drying time is about 0 to 110 ° C., for example, 5 seconds to
It takes about 60 minutes, preferably about 10 seconds to 30 minutes.

The thickness of the photosensitive layer provided on the support is 0.1 mm.
The range is preferably from 5 to 100 μm, in the case of a lithographic printing plate, from 0.5 to 5 μm, preferably from 1 to 3 μm, and when used for a dry film or the like, from 3 to 100 μm, preferably from 5 to 70 μm, more preferably It is in the range of 7 to 50 μm.

The thickness of the protective layer may be appropriately selected from a range satisfying the above-mentioned oxygen permeability.
The range is preferably 0.5 to 5 μm when a developable water-soluble polymer is used, more preferably 1 to 3 μm, and 10 to 50 μm for a water-insoluble polymer such as polyolefin. Preferably it is in the range of 15 to 45 μm. When the protective layer is formed by coating and drying, the protective layer is formed by applying and drying a solution in which a water-soluble polymer compound aqueous solution or a water-insoluble polymer compound is dissolved in a solvent as described above according to the photosensitive layer. Can be.

The light source for imagewise exposing the photosensitive resin laminate of the present invention includes carbon arc, high pressure mercury lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, halogen lamp, HeNe laser, argon ion laser, and YAG laser. , A HeCd laser, a semiconductor laser, a laser light source such as a ruby laser, and the like.
Is preferable, for example, a solid-state laser such as a ruby laser, a YAG laser, or a semiconductor laser can be mentioned. In particular, a small-sized and long-life semiconductor laser or a YAG laser is preferable. Usually, after scanning and exposure with these light sources, an image is formed by developing with a developer.

Examples of the developer used for developing the image-exposed photosensitive resin laminate include sodium silicate, potassium silicate, lithium silicate, ammonium silicate, sodium metasilicate, potassium metasilicate, sodium hydroxide, potassium hydroxide, and the like. Inorganic alkali salts such as lithium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium phosphate dibasic, sodium phosphate tribasic, ammonium phosphate dibasic, ammonium phosphate tribasic, sodium borate, potassium borate, ammonium borate, or Monomethylamine,
0.1 of organic amine compounds such as dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, monobutylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, etc.
An alkaline developer consisting of an aqueous solution of about 10 to 10% by weight is used. The developer may have nonionic properties as required.
Anionic, cationic, amphoteric or other surfactants or organic solvents such as alcohols may be added. In addition, development
The immersion development, spray development, brush development, ultrasonic development and the like are usually carried out at a temperature of preferably about 10 to 60 ° C, more preferably about 15 to 45 ° C.

[0068]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the present invention.

Example 1 An aluminum plate (0.24 mm thick) subjected to graining treatment and anodizing treatment was used as a support, and urethane acrylate (Kyoei) as an ethylenically unsaturated compound was formed on the surface of the aluminum plate support. UA-306 manufactured by
H); 20 parts by weight, ester acrylate (A-BPE-4 manufactured by Shin-Nakamura Chemical Co., Ltd.); 20 parts by weight, phosphate acrylate (PM-2 manufactured by Nippon Kayaku Co., Ltd.); 10 parts by weight, polymerization initiator 10 parts by weight; R-12 as a phthalocyanine infrared absorbing dye; 5 parts by weight; methyl methacrylate / methacrylic acid copolymer (copolymerization molar ratio of 7) as a binder. / 3
A weight-average molecular weight of 50000); 50 parts by weight of cyclohexanone; 850 parts by weight of a coating solution prepared by stirring at room temperature at room temperature using a wire bar, and dried at 70 ° C. for 1 minute to form a 2 μm-thick photopolymerizable film. A composition layer was formed. A 25 μm polyethylene film was laminated thereon and a protective layer was provided to produce a photopolymerizable lithographic printing plate.

The obtained photopolymerizable lithographic printing plate was coated with a diameter of 10
cm on a stainless steel rotating drum so that the protective layer is on the outside, and then the drum is rotated at 5 rpm, 50 rpm,
While rotating at four rotation speeds of 100 rpm and 200 rpm, scanning exposure was performed with a beam spot condensed to 30 μm using a semiconductor laser (“HL8325C” manufactured by Hitachi, Ltd.) having a wavelength of 830 nm and an output of 40 mW. After the protective layer was peeled off, it was developed by immersing it in a 1% by weight aqueous solution of sodium silicate at 25 ° C. for 60 seconds to form a scanning line image.

At this time, the sensitivity is evaluated based on the maximum number of rotations of the drum on which the line image is formed. Further, the edge portion of the image at the maximum number of rotations is observed with a microscope of 100 times, and the edges are sharply formed. Observing the resolution as “good” for those that are not good and “poor” for those that are not, and observing the non-image part (non-exposed part) at the maximum number of rotations in the same way, no background dirt is observed. Developability was evaluated as “good” and those with some stains as “poor”. Further, after the photopolymerizable lithographic printing plate was allowed to stand in a room illuminated by a white fluorescent lamp for 1 hour, an image was formed in the same manner, and the safelight property was evaluated. Sensitivity even when stored under white light,
Those with unchanged edge sharpness and developability were rated "good" for safelight properties, and those with poor sharpness and developability were labeled "bad".

Example 2 A photopolymerizable lithographic printing plate was prepared and evaluated in the same manner as in Example 1 except that the protective layer of the photopolymerizable lithographic printing plate of Example 1 was changed to a 25 μm polypropylene film.

Example 3 A photopolymerizable lithographic printing plate was prepared and evaluated in the same manner as in Example 1 except that the protective layer of the photopolymerizable lithographic printing plate of Example 1 was changed to a 25 μm polyethylene terephthalate film. .

Example 4 The protective layer of the photopolymerizable lithographic printing plate of Example 1 was added at 10 wt%.
Polyvinylpyrrolidone (same as in Example 1 except that an aqueous solution was applied with a wire bar and dried at 70 ° C. for 2 minutes to form a protective layer having a thickness of 3 μm and developed without removing the protective layer. To create a photopolymerizable lithographic printing plate,
evaluated.

Example-5 The protective layer of the photopolymerizable lithographic printing plate of Example 4 was added at 10 wt%.
A photopolymerizable lithographic printing plate was prepared and evaluated in the same manner as in Example 4 except that the vinylpyrrolidone / vinyl acetate copolymer (copolymerization molar ratio: 7/3) was used.

Example -6 The protective layer of the photopolymerizable lithographic printing plate of Example 4 was prepared by mixing vinylpyrrolidone / vinyl acetate copolymer (copolymer molar ratio: 7/3) and polyvinyl alcohol at a ratio of 5: 5 (weight ratio). A photopolymerizable lithographic printing plate was prepared and evaluated in the same manner as in Example 4, except that the photopolymerizable lithographic printing plate was formed using a 10 wt% aqueous solution blended in the above.

Comparative Example 1 The protective layer of the photopolymerizable lithographic printing plate of Example 4 was added at 10 wt%.
A photopolymerizable lithographic printing plate was prepared and evaluated in the same manner as in Example 4, except that the lithographic printing plate was formed using polyvinyl alcohol.

Comparative Example 2 The infrared absorbing dye of the photopolymerizable composition layer of the photopolymerizable lithographic printing plate of Comparative Example 1 was changed to a cationic dye (a cyanine dye manufactured by Nippon Kosoku Dye Co., Ltd.) (λmax 830n
A photopolymerizable planographic printing plate was prepared and evaluated in the same manner as in Example 4 except that m) was changed.

Comparative Example 3 The protective layer of the photopolymerizable lithographic printing plate of Comparative Example 2 was added at 10 wt%.
A photopolymerizable lithographic printing plate was prepared and evaluated in the same manner as in Example 4 except that the vinylpyrrolidone / vinyl acetate copolymer (copolymerization molar ratio: 7/3) was used.

Comparative Example 4 The infrared absorbing dye of the photopolymerizable composition layer of the photopolymerizable lithographic printing plate of Example 3 was converted to the following indoaniline compound (λmax)
A photopolymerizable lithographic printing plate was prepared and evaluated in the same manner as in Example 4 except that the thickness was changed to 800 nm).

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Embedded image

Table 1 summarizes the above results.

[0083]

[Table 1]

[0084]

According to the present invention, there is provided a photosensitive resin laminate having high sensitivity to light in the infrared region, good developability and resolution, and exhibiting safelight properties against white light. Can be provided. Therefore, according to the photosensitive resin laminate of the present invention, it is possible to directly draw a laser from a digital information of a computer using a low-power semiconductor laser or a YAG laser or the like, and to handle it in a bright working environment. Becomes possible.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) // H05K 3/02 H05K 3/02 B 3/10 3/10 CF term (reference) 2H025 AA00 AA01 AA02 AA04 AB03 AB15 AB17 AB20 AC08 AD01 BC12 BC14 BC31 BC34 BC43 BC51 CA00 CA39 CB52 CC11 CC13 DA03 FA10 FA17 2H096 AA06 AA26 AA27 AA28 BA05 EA04 GA08 5E339 BB02 BC10 BD14 BE05 CC10 DD02 DD03 5E343 AA02 AA11 BB60 DD68 GG08

Claims (6)

[Claims] 1. A photosensitive resin laminate comprising a support, on which a photosensitive layer containing an ethylenically unsaturated double bond-containing compound, a polymerization initiator and an infrared absorbing dye, and a protective layer are successively laminated. The external absorption dye is a phthalocyanine infrared absorption dye, and the oxygen transmittance of the protective layer is 1 × 10 ^-15 cm ³
(STP) · cm / cm ² · sec · cmHg｝ or more. 2. A photosensitive resin laminate comprising a support, on which a photosensitive layer containing an ethylenically unsaturated double bond-containing compound, a polymerization initiator and an infrared absorbing dye, and a protective layer are successively laminated. A photosensitive resin laminate, wherein the external absorption dye is a phthalocyanine infrared absorption dye, and the protective layer is an organic polymer film having a higher oxygen permeability than polyvinyl alcohol. 3. The phthalocyanine-based infrared-absorbing dye is 750
The photosensitive resin laminate according to claim 1, which is a phthalocyanine compound having a maximum absorption wavelength in a range from nm to 1200 nm. 4. The photosensitive resin laminate according to claim 1, wherein the photosensitive layer contains an alkali-soluble resin. 5. The photosensitive resin laminate according to claim 1, wherein the polymerization initiator is an organic boron complex. 6. A method for forming a negative image by imagewise exposing the photosensitive resin laminate according to claim 4 or 5 to alkali development.